JP6566588B2 - Polyamine addition compounds - Google Patents

Description

  Polymers containing amino groups, processes for their production, their use, and coating materials and plastics containing said polymers.

  The present invention relates to addition compounds and their salts which are suitable as dispersants and dispersion stabilizers. The present invention further provides methods for preparing these adducts, their use as dispersants and dispersion stabilizers for organic and inorganic pigments and fillers in organic and aqueous systems, and for incorporation into liquid systems. Solids in the form of powders or fibres, coated with such a dispersant. The subject of the invention is evident from the independent claims. The dependent claims relate to advantageous embodiments of the invention.

  Wetting agents present in the solution or dispersion reduce the surface tension or interfacial tension and therefore increase the wetting ability of the liquid. In many cases, wetting of the surface is only possible with such a wetting agent.

  In general, dispersants stabilize particulate solids in binders, paints, pigment pastes, plastics and plastic mixtures, adhesives and sealants, reduce the viscosity of such systems, and improve flowability. Suitable for. Dispersion stabilizers are used to stabilize dispersions that have already been produced.

  In order to be able to introduce the solid into the liquid medium, a strong mechanical force is required. In order to reduce the dispersion force and to minimize the overall input of energy into the system necessary to deagglomerate the particulate solid, and thus to minimize the dispersion time, It is customary to use dispersants. Such dispersants are anionic, cationic and / or neutral structure surfactants. These materials are applied in small amounts directly to the solid or added to the dispersing medium. It should be borne in mind that even after sufficient deagglomeration of the agglomerated solids into primary particles (after the dispersion operation), reagglomeration may occur, which may waste all or part of the attempt to disperse. is there. Typical results of inadequate dispersion and / or re-agglomeration include increased viscosity in liquid systems, color shifts and loss of gloss in paints and coatings, and reduced mechanical strength and uniformity of materials in plastics. This is an undesirable effect.

  Various types of compounds are actually suitable as wetting and dispersing agents. In particular, this is because, in particular, there are many different systems based on different types of binders in combination with different dispersed particles such as pigments, fillers and fibers. One class of materials that are widely applied as wetting and dispersing agents is that of side chain-containing polymers that include a core composed of polyethyleneimine. In this case, the side chains may be linked to the polyethyleneimine core by chemical bonds, as described, for example, in EP 1593700 and US 8268957. An alternative possibility is the formation of a salt between a polyethyleneimine core and acidic groups with side chains. These compounds are described for example in EP 0893155.

It is described in the aforementioned patent application, and polyamines described for the preparation of the dispersant is a linear or branched polyamines having a short alkylene bridge of C ₂ -C _4, such as polyethyleneimine. Wetting agents and dispersants produced with these polyamines have a high density of amine anchoring groups in the core. These groups, especially if not salified, can neutralize the acid catalyst in the case of acid-catalyzed coating formulations and therefore adversely affect the curing reaction. Furthermore, there are few technically available aliphatic-branched polyamines, so there is only a small possibility to achieve structural changes in structure, polarity, and amine density of the polyamine.

  Thus, over the prior art described above, the problem addressed by the present invention is to provide improved wetting and dispersing agents that have less impact on coating materials that are cured by acid catalysis. A further object is to replace polyethylenimine as a polyamine component of wetting agents and dispersants, e.g. an alternative that allows the realization of greater structural diversity in polyamines and thereby exhibits properties such as compatibility with various binders. To find things.

A method for solving this problem is a polymer PAS containing amino groups or a salt thereof obtained by reaction with an acid, wherein the polymer is obtained by multistage synthesis,
Intermediate PA is prepared by reaction of at least one compound P and at least amine A, wherein compound P contains 2 to 6 groups that are reactive towards hydroxyl and / or amino groups, A is
(I) primary and / or secondary amino groups with m = 1-8
(Ii) a hydroxyl group with n = 0-5, and (iii) a tertiary amino group with 1 = 0-5, where
(Iv) m + n ≧ 2,
(V) Compound A contains only a hydrocarbon group in addition to a nitrogen atom, an oxygen atom, and a hydroxyl group,
Intermediate PA is represented by the general formula (I)

[Where:
X ¹ = H or OH,
X ² = CH ₂ or C = O;
X ³ = O or NH]
Having structural units of
Intermediate PA is
(A) reacting with one or more components S that are reactive towards hydroxyl groups and / or amino groups to give polymers containing amino groups, and / or (b) at least one lactone or Reacting with a mixture of lactones in a ring-opening polymerization to give a polymer containing amino groups, and (c) 0-80% of the primary and secondary amino groups originally present in the intermediate PA Reacting with one or more species of component U selected from the group of cyclic compounds selected from the group of hydroxyl functional acrylates and / or oxiranes and oxetanes, lactones, and cyclic carbonates, Occurs by the introduction of hydroxyl groups,
The reactions (a), (b), and (c) are polymers PAS containing amino groups or salts thereof obtained by reaction with an acid, which may be carried out in any desired combination and time series with each other. .

As a symbol

Means that the structure shown is linked to a higher order general structure.

Compound P is reactive to hydroxyl and / or amino groups and usefully contains 2 to 6, preferably 2 to 3, more preferably 2 groups, which are acrylates , Epoxides, carboxylic acids, and carboxylic acid esters, usefully selected from the group of carboxylic acid derivatives such as carboxylic acid chlorides and carboxylic acid anhydrides, with carboxylic acid esters being particularly preferred among the group of carboxylic acid derivatives. The upper limit of the number average molecular weight (M _n ) of P is usefully 1000, preferably 600, more preferably 300, and very preferably 250.

Preferred compounds A primarily comprise a methylene group — (CH 2) n —, where n is usefully 1-6, preferably 2-3, more preferably 2. A contains at least 1, preferably 2, and more preferably 3-5 amino groups. The maximum value of amino groups is 8, preferably 6, and more preferably 5. The upper limit of the number average molecular weight (M _n ) of A is usefully 2000, preferably 1000, more preferably 600, very particularly preferably 300, and particularly preferably 250.

Examples of suitable amine-containing compounds A are, inter alia, aliphatic, cycloaliphatic, aliphatic / alicyclic mixtures, aromatic and / or araliphatic diamines and / or polyamines, or two or more of these It is a mixture containing the amine. Examples of these are ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine, hexaethylene pentamine, and higher homologs, general formula _NH 2 _- the higher linear condensates of _{(C 2 H 4 NH) n} -C 2 H 4 -NH 2 (n <7) Product, dipropylenetriamine, bis (hexamethylene) triamine, 3- (2-aminoethyl) aminopropylamine, N, N-bis (3-aminopropyl) methylamine, tetramethyliminobispropylamine, N, N- Dimethyldipropylenetriamine, bis (3-dimethylaminopropyl) a And N, N′-bis (3-aminopropyl) ethylenediamine, tris (3-aminopropyl) amine, tris (2-aminoethyl) amine; other examples are isophorone diamine, Primea 1074 from Croda, 4,4′-diaminodiphenylmethane, 1,3- and 1,4-xylylenediamine, 4,4′-diaminodicyclohexylmethane, 1,4-bis (aminomethyl) cyclohexane, low molecular weight polyether having an amino group, etc. Of polyalkylene oxide-based diamines and / or polyamines such as Jeffamine® polyoxyalkyleneamine sold under the trade name Huntsman: D-230, D-400, D -2000, XTJ-510, X J-500, XTJ-501, XTJ-502, XTJ-504 (Jeffamin EDR 148), HK-511, T-403, XTJ-509, and a T-5000.

  In addition to primary or secondary amines, such as primary or secondary amines and / or alcohols, examples of amine-containing compounds A that contain additional groups that are reactive towards esters include diethylenetriamine and the like In addition to the primary amino group and the compound having three primary or secondary amino groups, it contains at least one further group that is reactive towards the ester, or contains a secondary amino group In addition, amines containing at least two additional groups that are reactive towards esters, such as monoethanolamine, 2-amino-2- (hydroxymethyl) -1,3-propanediol, 2- (2- Aminoethoxy) ethanol, aminoethylethanolamine, 2-amino-2-desoxy-D-glucose chitosamine, and diethanolamine. .

  It is likewise possible to use mixtures of these compounds as component A.

  Polyamine PA can be produced by various synthetic routes.

Option 1
According to this synthetic route, polyamine PA is constituted by the reaction of component P and component A. The polyamine PA is constituted by a reaction in which the building block CG _h (where h = 2-8) is used or formed during the reaction from amine A and component P. The structural unit CG _h has at least one carboxylic ester group C ′ and at least two groups G ′ that are reactive towards the carboxylic ester group C ′. If one is not amine structural unit CG _h also _includes at least a tertiary amine in its structure.

  The theory of construction of branched polyamines shown in Option 1 is described, for example, in Prog. Polym. Sci. 29 (2004) pages 183-175, section 3.4, pages 208-212, described by Gao and Yan.

The CG _h molecule, in option 1, comprises a component P selected from the group of ethylenically unsaturated ester compounds, wherein the C = C double bond and the ester carbonyl double bond are conjugated, and a primary or second In addition to primary or secondary amines, such as secondary amines and / or alcohols, amines A selected from diamines or groups of amines containing 2 to 7 additional groups that are reactive towards esters, and It can comprise by reaction of these. Routes for obtaining branched polyamines are described, for example, in CN021111578.8, WO2011 / 077675, and WO2012 / 175622. In WO2011 / 077675 and WO2012 / 175622, a plurality of ester groups are attached to component P. Only the use of α, β-unsaturated esters is described.

Examples of component P according to option 1 selected from the group of ethylenically unsaturated ester compounds in which the C = C double bond and the carbonyl double bond of the ester are conjugated are, for example, methyl acrylate, ethyl acrylate Alkyl acrylates such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and lauryl acrylate ;
Tetrahydrofurfuryl acrylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acrylate, cyclohexyloxymethyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethyl acrylate, furfuryl acrylate, 2-butoxyethyl acrylate, 2 Monoacrylates of short chain ethers such as ethoxyethyl acrylate, allyloxymethyl acrylate, 1-ethoxybutyl acrylate, 1-ethoxyethyl acrylate, ethoxymethyl acrylate;
Maleic acid diesters such as dimethyl maleate, diethyl maleate, and dibutyl maleate;
Fumaric acid diesters such as dimethyl fumarate, diethyl fumarate, and dibutyl fumarate;
Itaconic acid esters such as dimethyl itaconate and diethyl itaconate.

  It is likewise possible to use mixtures of these compounds as component P under option 1.

  Preferred component P in option 1 is a compound selected from the group of acrylate esters; more preferred are short chain alkyl acrylates, particularly preferred are methyl acrylate and ethyl acrylate.

  Component P and amine A are usefully 1: 0.5 to 1: 3, preferably 1: 0.8 to 1: 2, more preferably 1: 1 to 1: 1.7, very preferably 1: Used in a molar ratio of 1.01-1: 1.5.

The size of polyamine PA under Option 1 is
1) For example, change of reaction conditions such as selection of solvent 2) Control can be performed by the molar ratio of amine A to component P.

The construction of the polyamine PA under option 1 is carried out, for example, in two steps. In the first step, CG _h building blocks are manufactured. The CG _h building block is composed of a Michael addition of a primary or secondary amino group to a C═C double bond conjugated to an ester carbonyl double bond. These reactions are usefully carried out in the temperature range of 0-100 ° C, preferably 10-80 ° C, more preferably 15-50 ° C. Michael addition may be carried out without solvent or in suitable polar and nonpolar solvents. Suitable solvents are those in which the reactants and reaction products are at least partially soluble. The solvent may remain in the product or may be removed. When removing the solvent, it is useful to use a volatile solvent. Water and low molecular weight alcohols such as, for example, methanol, ethanol, propanol, isopropanol, and butanol can be readily removed in subsequent steps of the synthesis or in its application, for example using distillation.

  The monitoring of the Michael addition reaction can be performed by NMR measurements, including monitoring the conversion of the C═C double bond conjugated to the ester carbonyl double bond.

  The product of Michael addition is subsequently polycondensed to form polyamine PA. These reactions are usefully carried out in the temperature range of 50-180 ° C, preferably 70-160 ° C, more preferably 80-150 ° C. The alcohol formed from the cleavage of the carboxylic acid ester, and optionally the solvent used, is removed from the reaction mixture. If water is selected as the solvent, the size of the resulting polyamine should be lower than, for example, in the absence of an alcohol solvent or solvent. This is because there is a partial conversion of the ester to the carboxylic acid, and the carboxylic acid forms a salt with the amino group.

If the CG _h building blocks used for polycondensation do not contain compounds with any amine-based groups that are reactive towards esters, polycondensation can be carried out, for example, tetrabutyl titanate, zirconium butoxide, zirconium propoxide, Alternatively, it is carried out using a catalyst such as zirconium acetylacetonate. What is described in the literature is, for example, para-toluenesulfonic acid (X. Wang, X. Yuan, T. Qiang, X. Chen, e-Polymers 2009, 115, 1-15) or zinc acetate and tetrabutyl It is the structure of such a structure using various catalysts such as titanate (C. Gao et al., Biomacromolecules 2003, 4, 704-712).

  The polycondensation may be carried out with or without the addition of core molecules. Examples of core molecules are ammonia or amines suitable as amine A. Preferred amines are compounds containing 2-3 primary amino groups such as, for example, tris (2-aminoethyl) amine and tris (3-aminopropyl) amine. When polycondensation is carried out using a catalyst, compounds containing hydroxyl groups are also suitable as core molecules. These compounds usefully contain 1 to 6 hydroxyl groups. Examples of core molecules containing hydroxyl groups are 1,1,1-trimethylolpropane, triethanolamine, glycerin, diglycerin, triglycerin, 1,3,5-tris- (2-hydroxyethyl) cyanuric acid, and Sorbitol.

In this case, the size of the polyamine PA can be controlled by the molar ratio of the core molecule to the CG _h constituent unit.

Option 2
In addition to the polyamine PA produced by one-stage condensation under option 1, the polyamine PA may be similarly constructed in a shell formula by stepwise synthesis starting from the same components A and P. For this purpose, in contrast to option 1, components A and P are used alternately in excess in a synthesis sequence of two alternating stages, and after each stage the excess is removed by distillation. The stepwise composition of the resinous polyamidoamine is described in, for example, A. By Tomalia et al., Polymer Journal 1985, 17, 117-132 and US Pat. No. 4,568,737.

  In this case, the resinous polyamine PA is prepared by a two-step synthesis sequence starting from ammonia or from an amine A such as ethylenediamine. The first stage of the synthesis involves complete reaction of the amine core with excess alkyl acrylate as component P, such as methyl acrylate, for example using Michael addition, and removal of unreacted alkyl acrylate. The second stage involves complete reaction of the resulting ester with excess diamine as component A, such as ethylenediamine, and removal of excess diamine used. The sequence in which these two steps are repeated constitutes the polyamine PA step by step.

  Examples of suitable amine-containing compounds A in option 2 are in particular aliphatic, cycloaliphatic, aliphatic / alicyclic mixtures, aromatic and / or araliphatic diamines, or two or more of these amines. It is a mixture containing. Examples of these are ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-hexamethylenediamine.

  The preferred component A in Option 2 is a relatively volatile diamine so that these can be easily removed. Particularly preferred are ethylenediamine and 1,2- and 1,3-diaminopropane.

  Examples of Option 2 component P, selected from the group of ethylenically unsaturated ester compounds in which a C═C double bond and an ester carbonyl double bond are conjugated, are for example methyl acrylate, ethyl acrylate, Alkyl acrylates such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. It is also possible for component P of option 2 to use a mixture of these compounds as well.

  The preferred component P in option 2 is a relatively volatile acrylate so that these can be easily removed. Particularly preferred are methyl acrylate and ethyl acrylate.

Option 3
Production of a polyamine PA by reaction of an amine-containing compound A and a compound P, wherein the compound P contains 2 to 6 groups that are reactive towards amino groups and is an epoxide epoxide, such as an acrylate and / or the like Production of a polyamine PA, selected from the group of For example, it is possible to use a compound having a glycidyl acrylate group and an acrylic acid group. Some of the amino groups of A may react with monofunctional acrylates and / or epoxides. These monofunctional compounds in each case usually contain a total of 6 to 70 carbon atoms.

  A number of carbon atoms less than 6 results in excess polarity, while more than 70 carbon atoms usually harm general compatibility.

  These reactions are usefully carried out in the temperature range of 20 to 140 ° C., preferably 120 ° C. or less, more preferably 100 ° C. or less.

  In the reaction with the epoxide, a secondary or tertiary amino group is formed on the secondary hydroxyl group and on the nitrogen atom involved in the reaction.

  Examples of polyfunctional acrylates include di, tri, tetrafunctional polyesters, polyethers, polyether / esters, urethane or epoxy acrylates, mono, di, tri or polyalkylene glycol diacrylates such as mono, Di, tri or polyethylene glycol diacrylate, mono, di, tri or polypropylene glycol diacrylate, butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, neopentyl glycol propyleneoxy Diacrylate, tricyclodecanediol diacrylate, glycerol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate Over DOO, pentaerythritol triacrylate, there is dipentaerythritol pentaacrylate, and the like.

  Examples of multifunctional epoxides include mono, di, tri or polyalkylene glycol diglycidyl ethers, such as mono, di, tri or polyethylene glycol diglycidyl ether, propanediol diglycidyl ether, di, tri or polypropylene glycol diglycidyl Ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, di-, tri- or polyglycerol triglycidyl ether , Trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether There is an ether and the like.

  Examples of monofunctional acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, tert-butyl. Acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, lauryl acrylate, etc .; short chain ether monoacrylates such as tetrahydrofurfuryl acrylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acrylate, cyclohexyloxy Methyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethyl acrylate, furfuryl acrylate, 2-butoxyethyl acrylate, 2-ethoxyethyl acrylate, acrylate Oxy methyl acrylate, 1-ethoxy butyl acrylate, 1-ethoxyethyl acrylate, there is ethoxymethyl acrylate.

Suitable monofunctional epoxides include aliphatic, cycloaliphatic and / or aromatic glycidyl ethers such as C _{1 to} C ₂₀ alkyl glycidyl ethers, phenyl glycid ethers, cresyl glycidyl ethers, naphthyl glycidyl ethers, Butyl glycid ether, p-tert-butylphenyl glycid ether, 2-ethylhexyl glycid ether, C _{12 to} C ₁₄ glycid ether, allyl glycidyl ether, 2,3- Epoxypropyl neodecanoate (Cardura (registered trademark) E10, Resolution Performance Products).

The polymer PAS of the present invention is a polyamine PA,
(A) reacting with one or more components S that are reactive towards hydroxyl and / or amino groups to give polymers containing amino groups and / or (b) at least one lactone Or reacting with a lactone mixture by ring-opening polymerization to give a polymer containing amino groups, and (c) 0-80% of the primary and secondary amino groups originally present in the intermediate PA, Reacting with hydroxyl functional acrylate and / or one or more species of component U selected from the group of cyclic compounds selected from the group of oxiranes and oxetanes, lactones and cyclic carbonates, said reaction comprising hydroxyl Caused by the introduction of groups,
The reactions of (a), (b), and (c) are prepared by a procedure that may be performed in any desired combination and time series with each other.

  In this case, polyamine PA can be reacted with one or more reactive components S specified below. Polyamine PA may also be reacted with one or more components U specified below.

  Component S and optionally U is at least 10% of the reactive groups originally present in the intermediate PA, usefully at least 25%, preferably at least 50%, more preferably at least 75%, most preferably all It is used in such an amount that it can react.

Ingredient U includes:
a) Hydroxyl functional acrylate Suitable hydroxyl functional acrylates are, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, 2 -Hydroxy-3- [3- (trimethoxysilyl) propoxy] propyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, for example, a variant AE sold by NOF under the trade name BLEMMER® -90, AE-200, and polyethylene glycol acrylates such as AE-400, for example, variants AP-150, AP-400, and AP-550 such as variants sold by NOF under the trade name BLEMMER®. Ripropylene glycol acrylate, and lactone-modified hydroxyethyl acrylate such as, for example, a FA variant sold by Daicel Corporation under the trade name Placcel.
b) Oxirane and / or Oxetane Suitable oxiranes are, for example, C _{1 to} C ₂₀ alkyl glycidyl ethers, phenyl glycidyl ethers, cresyl glycidyl ethers, naphthyl glycidyl ethers, butyl glycid ethers, p-tert-butylphenyl glycid ether, 2-ethylhexyl glycid ether, C _{12 to} C ₁₄ glycid ether, allyl glycidyl ether, or 2,3-epoxypropyl neodecanoate ( Aliphatic, alicyclic and / or aromatic glycidyl ethers such as Cardura E10, Resolution Performance Products). Monofunctional epoxides are preferred. Reaction with the epoxide produces secondary hydroxyl groups and secondary or tertiary amino groups on the nitrogen atoms involved in the reaction.
Suitable oxetanes are, for example, 3-ethyl-3- (phenoxymethyl) oxetane and 3-ethyl-3- (hydroxymethyl) oxetane.
c) Lactones Suitable lactones are, for example, propiolactone, valerolactone, butyrolactone, caprolactone and / or substituted lactones. Preferred lactones are ε-caprolactone and δ-valerolactone.
d) Cyclic carbonates Suitable cyclic alkene carbonates have 5 or 6 membered rings and may be optionally substituted. Suitable substituents are aliphatic, alicyclic and / or aromatic groups having up to 30 carbon atoms. Suitable cyclic carbonates are, for example, ethylene carbonate, propylene carbonate, glycerol carbonate, 5-methyl-5-propyltrimethylene carbonate, trimethylene carbonate, 4-methyltrimethylene carbonate, 5-methyltrimethylene carbonate. 5,5-dimethyltrimethylene carbonate or 5,5-diethyltrimethylene carbonate.

  As component U, mixtures of these compounds can be used as well.

Ingredient S includes:
a) General formula (II)
Y—O—CO—NH—R ¹ —NCO (II)
Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms.
Isocyanate adduct. The reaction of component S of general formula (II) requires the presence of primary and / or secondary amino groups and / or alcohol groups.
b) General formula (III)

Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms.
Uretdione compounds. The reaction of component S of general formula (III) requires the presence of primary and / or secondary amino groups.
c) General formula (IV)
_{H 2 C = CH-COO-} Y (IV)
Acrylate. The reaction of component S of general formula (IV) requires the presence of primary and / or secondary amino groups.
d) An acid selected from the group of sulfonic acids, carboxylic acids and phosphate esters of general formula (VII). Preference is given to carboxylic acids of the general formula (V) and phosphate esters of the general formula (VI).
_{^{(HOOC) p -Y (X 1}} ) r (V)
(OH) _{3 -V} PO (OY (X ¹ ) _r ) _v (VI)
Y—SO ₂ —OH (VII)
[Wherein p = 1 to 3, r = 1 to 5, X ¹ = H or OH, and v = 1 or 2]

  The reaction of component S of the general formula (V) requires the presence of primary and / or secondary and / or tertiary amino groups and / or alcohol groups.

  The reaction of component S of general formula (VI) requires the presence of primary and / or secondary and / or tertiary amino groups.

  The reaction of component S of general formula (VII) requires the presence of primary and / or secondary amino groups.

  Other options for side chain construction are, for example, polyamine PA or modified polyamine PA and propiolactone, valerolactone, butyrolactone, as will be described later in the specification with respect to the synthesis of monofunctional polyesters later. Reaction by ring-opening polymerization with a lactone such as caprolactone and / or a substituted lactone. Similarly, it is possible to use a mixture of different lactones.

  Modified polyamine PA here and below represents a polyamine obtained from PA by one or more of reactions (a), (b), and (c), which is primary and / or secondary It still contains reactive groups such as amines and / or hydroxyl groups.

  Usually Y comprises at least one polyether group, polyester group, hydrocarbon group and / or polysiloxane group.

  Often Y preferably contains ether oxygen atoms and contains a total of 1 to 450 ether oxygen atoms present in groups derived from polytetrahydrofuran, polyoxetane and / or polyoxirane.

  Typically, Y contains a total of 3 to 400 ether oxygen atoms, and at least 50, preferably at least 80 mol% of the ether oxygen atoms are present in the ethylene oxide and / or propylene oxide structural units.

  The alcohol Y-OH used in the process of the present invention may have further heteroatoms such as O, S, Si and / or N and / or ether, urethane, carbonate, amide, urea and / or Alternatively, it may contain an ester group. In the Y group, hydrogen is optionally substituted by halogen (eg, fluorine and / or chlorine). The Y group may have additional groups such as C═C double bonds, which act inertly in the formation of the addition product. The ester, ether, urethane, carbonate and / or siloxane groups that may be present may take a block structure (eg, poly (ethylene oxide-block-propylene oxide-block-ε-caprolactone) or form a gradient. It may be well or randomly arranged.

1) For ether groups or polyethers that may be present in Y:
As Y-OH, it is possible to use monohydroxy polyethers. These include, for example, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, isopropyl glycid ether, Alkoxyls with aliphatic or aromatic glycid ethers such as glycid ether, allyl glycid ether, 2-ethylhexyl glycid ether, cresyl glycid ether, and phenyl glycidyl ether It may be manufactured by chemical conversion. Mixtures of these raw materials may be used. In the case of mixed polyethers, these may be arranged randomly, in a gradient form, or in blocks. These polyethers often have a number average molecular weight ( _Mn ) in the range of about 100 to 25000, particularly often 150 to 15000, particularly typically 200 to 10000 g / mol. Preferred polyethers are those based on ethylene oxide, propylene oxide, and mixtures thereof.

Examples include hydroxyl functional vinyl compounds such as hydroxybutyl vinyl ether, allyl polyethers (eg, Polyglycol A 350, Polyglycol A 500, Polyglycol A 1100, Polyglycol A 11-4, Polyglycol A 10-4, or Polyglycol A 20g, manufactured by Clariant AG). Pluriol (registered trademark) A 010 R, Pluriol (registered trademark ⁾ A 11 RE, Pluriol (registered trademark) A 13 R, Pluriol (registered trademark) A 22 R or Pluriol (registered trademark) manufactured by BASF AG ) A 23 R), vinyl polyethers (eg, Polyglycol V 500, Polyglycol V 11 from Clariant AG) 0 or Polyglycol V 5500), polyoxyethylene monoalcohol initiated from methanol (eg Pluriol® A 350 E, Pluriol® A 500 E, Pluriol® A 750 E from BASF AG , Pluriol® A 1020 E, Pluriol® A 2000 E or Pluriol® A 5010 E), polyoxypropylene monoalcohols initiated from alcohols (eg, Polyglycol B01 / 20 from Clariant AG) , Polyglycol B01 / 40, Polyglycol B01 / 80, Polyglycol B01 / 120 or Polyglycol B01 / 240, or BASF Pluriol® A 1350 P from G or Pluriol® A 2000 P) and polyalkoxylates with various degrees of alkoxylation, starting with various fatty alcohols (trade name Lutensol from BASF AG) (Registered trademark) A, Lutensol (registered trademark) AT, Lutensol (registered trademark) AO, Lutensol (registered trademark) TO, Lutensol (registered trademark) XP, Lutensol (registered trademark) XL, Lutensol (registered trademark) AP and Lutensol ( Monohydroxy-functional polyoxyalkylene monoalcohols such as (registered trademark) known as ON). Preferred for use are polyoxyalkylene monoalcohols containing ethylene oxide and / or propylene oxide and / or butylene oxide groups, optionally modified with styrene oxide. Particularly preferred are polyoxyalkylene monoalcohols (for example, Polyglycol B 11/50, Polyglycol B 11/70, Polyglycol B 11/100, Polyglycol B 11/150, or Polyglycol B 11/11 or P / 700, use of Pluriol® A 1000 PE, Pluriol® A 1320 PE, or Pluriol® A 2000 PE from BASF SE, or Terralox WA 110 from DOW Chemicals. Polyoxyalkylene starting from butanol consisting of ethylene oxide and propylene oxide and having terminal OH groups It is.

2) Regarding hydrocarbon groups that may be present in Y:
The hydrocarbon group preferably takes the form of an aryl group, a branched or unbranched alkylaryl group, an aralkyl group and / or an acyclic, cyclic branched or unbranched alkyl group. Possible is also the use of such compounds, ie a mixture of at least two different compounds Y- (OH). The aliphatic or araliphatic compound Y- (OH) may be linear or branched, saturated or unsaturated. Saturated species are preferred.

  Examples of Y-OH having a hydrocarbon group include methanol, ethanol, propanol, isopropanol, butanol, ethyl hexanol, decanol, isotridecyl alcohol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, benzyl alcohol, propargyl alcohol, oleyl There are alcohols, linoleyl alcohol, oxo alcohols, neopentyl alcohol, cyclohexanol, fatty alcohols, alkylphenols, alkylnaphthols and phenylethanol.

  In addition, Y-OH may be a non-hydrogenated, partially hydrogenated and / or fully hydrogenated polybutadiene, non-hydrogenated, partially hydrogenated and / or fully hydrogenated polyisoprene, polyisobutylene, polypropylene or ethylene / butylene copolymer. Polyolefin monools such as These compounds are known. For example, a route for obtaining hydroxyl-functional polyisobutylene is described in US6875588.

3) For ester groups or polyesters that may be present in Y:
It is also possible to use monohydroxy monoesters and monohydroxy polyesters as Y-OH.

  Hydroxy functional acrylates or methacrylates, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxybutyl (meth) acrylate are examples of suitable monohydroxy monoesters.

  Polyesters can be esterified, for example, by dicarboxylic acids such as anhydrides, acyl chlorides, or dialkyl esters (eg, dimethyl esters or diethyl esters) by reaction with diols and mono-, di- or trifunctional initiators. It can be produced by reaction of a derivative. The formation of dihydroxy polyester may be inhibited using an appropriate stoichiometric amount of monohydroxy compound if desired. Esterification may be carried out in bulk or by azeotropic esterification in the presence of an azeotrope forming agent. Examples of dicarboxylic acids are succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid, or dimerized fatty acids and their isomers and hydrogenation products. Examples of corresponding diols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cis-1,2-cyclohexanedi Polyglycols based on methanol, trans-1,2-cyclohexanedimethanol, and ethylene glycol and / or propylene glycol.

Preferred polyesters for use as Y-OH are (as described in US Pat. No. 4,647,647) polycondensation of one or more optionally substituted hydroxycarboxylic acids, optionally substituted with alkyl, and / or Those obtained by ring-opening polymerization of the corresponding lactone, such as propiolactone, valerolactone, butyrolactone, caprolactone and / or substituted lactone, using a monohydroxy initiator. These preferably have a number average molecular weight (M _n ) of 150 to 5000 g / mol. As starting component, any other compound listed as Y-OH can in principle also be used. In any case, it is also possible to use mixtures of the aforementioned compounds. Lactone polymerization is carried out at a temperature of about 70 ° C. to 180 ° C. by known methods, for example initiated with titanate, p-toluenesulfonic acid or dibutyltin dilaurate. Particularly preferred are polyesters based on ε-caprolactone, optionally in combination with δ-valerolactone.

4) For polycarbonates that may be present in Y:
The Y group may comprise a carbonate group obtained by known reactions with acyclic and / or cyclic carbonates. Suitable are, for example, carbonate-modified linear polyesters or polycarbonate diols used in the production of polyurethanes. Examples are described in US-4101529. Suitable carbonates are aliphatic, cycloaliphatic, araliphatic and / or dialkyl carbonates such as, for example, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate, catechol carbonate, or cyclic alkylene carbonate. Or it is an aromatic carbonate. Particularly suitable are optionally substituted cyclic alkylene carbonates having a 5- or 6-membered ring. Preferred substituents are aliphatic, alicyclic and / or aromatic groups having up to 30 carbon atoms. Examples of suitable cyclic alkylene carbonates are ethylene carbonate, propylene carbonate, glycerin carbonate, trimethylene carbonate, 4-methyltrimethylene carbonate, 5-methyltrimethylene carbonate, 5,5-dimethyltrimethyl. Methylene carbonate, 5,5-diethyltrimethylene carbonate, or 5-methyl-5-propyltrimethylene carbonate.

5) For polyoxazolines that may be present in Y:
As Y-OH, a hydroxyl-functional poly-2-alkyl-2-oxazoline or poly-2-alkyl-2-oxazine can also function. It is preferred to use monohydroxy functional compounds. Poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines can be prepared by initiators such as para-toluenesulfonic acid, methyl tosylate, or methyl triflate with 2-alkyl-2-oxazolines or 2- It is obtained by cation and ring-opening polymerization of alkyl-2-oxazine. Oxazolinium or oxazinium end groups obtained from living cationic polymerization mechanisms may be converted to more stable hydroxyamides by aminoester end groups by alkaline hydrolysis. An alternative route to produce monohydroxy functional poly-2-alkyl-2-oxazoline or poly-2-alkyl-2-oxazine is the starting species as 2- (4-hydroxyphenyl) -N-methyl-2- Polymerization with oxazolinium trifluoromethanesulfonate (A. Gross. G. Maier, O. Nuyken, Macromol. Chem. Phys. 197, 2811-2826 (1996)). The choice of alkyl substituents can control the compatibility, for example, poly-2-ethyl-2-oxazoline has water solubility suitable for highly polar systems, while for example poly-ethyl- 2-Lauryl-2-oxazoline is compatible in nonpolar systems. When block copolymers of 2-ethyl-2-oxazoline and 2-lauryl-2-oxazoline are formed, the polymer is particularly prominent in wide compatibility. Such poly-2-alkyl-2-oxazoline or poly-2-alkyl-2-oxazine usually has a number average molecular weight ( _Mn ) of 300 to 20000 g / mol, preferably 500 to 10,000 g / mol. In particular, it is possible to use different types of 2-oxazolines, which may optionally have additional functional groups. An example of such a species is 2-oxazoline based on the corresponding fatty acid.

6) For OH functional polymers of ethylenically unsaturated compounds that may be present in Y:
It is also possible to use an OH-functional polymer of an ethylenically unsaturated monomer that does not have an OH functional group as Y-OH. The OH functional group can be introduced in a known manner via an initiator or chain transfer agent. Such compounds are already used in the art for the production of other dispersants, as described in US-A-4032698 or EP 318999. These polyacrylates usually have a number average molecular weight ( _Mn ) of 300 to 20000 g / mol, preferably 500 to 10000 g / mol. These may be arranged in a block structure or randomly, or may form a gradient.

  Examples of ethylenically unsaturated monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate Straight chain having 1-22 C atoms, such as 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and t-butyl (meth) acrylate Alkyl (meth) acrylates of branched, branched, or alicyclic alcohols; benzyl methacrylate or phenyl acrylate (wherein the aryl group is either unsubstituted or substituted up to 4 times) Aryl (meth) acrylates such as For example, 4-nitrophenyl methacrylate; tetrahydrofurfuryl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, cyclohexyloyl methyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate Sulfonate, 2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate, poly (ethylene glycol) methyl ether (meth ) Acrylate, poly (propylene glycol) methyl ether (meth) acrylate, etc., ethers having 5 to 80 C atoms, Mono (meth) acrylates of ethylene glycol, polypropylene glycol, or mixed polyethylene / propylene glycol; N, N-dimethylaminoethyl (meth) acrylate, 2-trimethylaminoethyl methacrylate chloride, and N, N-dimethylaminopropyl (meth) ) Aminoalkyl (meth) acrylates such as acrylates; (meth) acrylates of halogenated alcohols such as perfluoroalkyl (meth) acrylates having 6 to 20 C atoms; Styrenes such as 4-methylstyrene and substituted styrenes Methacrylonitrile and acrylonitrile; ethylenically unsaturated heterocycles such as 4-vinylpyridine and 1- [2- (methacryloyloxy) ethyl] -2-imidazolidinone; vinyl acetate Vinyl esters of carboxylic acids having 1 to 20 C atoms such as: maleimide, N-phenylmaleimide, and straight chain having 1 to 22 C atoms, such as N-ethylmaleimide and N-octylmaleimide, N-substituted maleimides having branched or alicyclic alkyl groups; (meth) acrylamides; straight chain having 1 to 22 C atoms, such as N- (tert-butyl) acrylamide and N, N-dimethylacrylamide, N-alkyl- and N, N-dialkyl substituted acrylamides having branched or alicyclic alkyl groups.

  Preferred non-OH functional monomers are alkyl (meth) acrylates, aryl (meth) acrylates, and styrene.

7) For polysiloxanes that may be present in Y:
It is also possible to use monohydroxy-functional polysiloxanes as Y-OH. Polysiloxane has the following general formula:

[Where:
T = C ₁ -C ₁₄ alkylene,
Aliphatic and / or fat having an unbranched polyether group consisting of alkylene oxide units with RK = 1 to 6 carbon atoms, and / or a number average molecular weight (M _n ) between 130 and 2700 g / mol Cyclic and / or aromatic polyester groups,
R ¹³ and R ¹⁴ are each independently C ₁ -C ₁₄ alkyl, aryl or aralkyl, —O (C ₁ -C ₁₄ alkyl, aryl or aralkyl), —OCO (C ₁ -C ₁₄ alkyl). , Aryl or aralkyl), —O—CO—O (C ₁ -C ₁₄ alkyl, aryl or aralkyl), —OSO ₂ (C ₁ -C ₁₄ alkyl, aryl or aralkyl), —H, —Cl, —F , -OH, -R, -RK,
R ¹⁵ = C ₁ -C ₁₄ alkyl, aryl, or aralkyl,
R ¹⁶ = a polyhydroxy-functional branched polyglycidol polyether group consisting of or comprising a branched polyglycidol group;
A = 0-20, preferably 1-15, more preferably 1-8,
B = 2 to 300, preferably 10 to 200, more preferably 15 to 100,
C = 0-20, preferably 1-15, more preferably 1-8,
Here, when C = 0, R ¹⁴ = R ¹⁶ and / or R ¹³ = R ¹⁶ , and when a — [SiR ¹⁵ (Z—R ¹⁶ )] — O— unit is present, ie, C is When at least 1, R ¹³ and R ¹⁴ can be different from R ¹⁶ ]
Can be described by:

  The described polysiloxane groups may also be present in the form of organically modified polysiloxane groups.

The isocyanate adduct of the general formula (II) is diisocyanate R ¹ (NCO) ₂ containing an NCO group having different reactivity with Y—OH, and is at least equal to the hydroxyl component Y—OH. Synthesized by reaction with diisocyanate R ¹ (NCO) ₂ used in molar ratio or in excess. If diisocyanate R ¹ (NCO) ₂ is used in excess, it must be removed after the reaction. For this purpose, for example, distillation is suitable.

When diisocyanate R ¹ (NCO) ₂ containing NCO groups with different reactivities is used in molar excess, preferably in the sense that only exactly one NCO group of the diisocyanate reacts with Y—OH. Bring higher selectivity. The higher the molar excess of diisocyanate, usually the higher the selectivity for the production of isocyanate adduct (II). As a result of its use, the unreacted diisocyanate obtained in excess is correspondingly at least partly (as complete as possible) removed from the reaction mixture. This is because in the case of further reaction with polyamine PA or modified polyamine PA, this diisocyanate causes high molecular weight products due to undesirable crosslinking. The synthesis of this type of isocyanate adduct (II) is described, for example, in WO2012 / 175159 or EP1048681.

  Depending on the reactivity of the individual reaction partners, the isocyanate addition may be carried out in the usual temperature range for this type of reaction from room temperature to about 150 ° C., preferably 100 ° C., more preferably 70 ° C. Tertiary amine, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N′-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2.2.) For the purpose of promoting and suppressing secondary reactions. 2) Octane and, in particular, iron compounds such as titanate esters, iron (III) acetylacetonate, organometallic compounds such as tin compounds, for example tin diacetate, tin dioctate, tin dilaurate, or dibutyltin diacetate Known and customary catalysts such as dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids, such as dibutyltin dilaurate, can be used. These catalysts are usually used at 0.0001 to 0.1 parts by weight per 100 parts by weight of diisocyanate.

Depending on the viscosity, the reaction may be carried out in bulk or in the presence of a suitable solvent, solvent mixture, or other suitable carrier medium. Suitable solvents or carrier media are all non-reactive under the chosen reaction conditions or whose reactivity is negligible compared to the reaction partner, among which the reactants and reactions The product is at least partially soluble. These include, for example, hydrocarbons such as toluene and xylene, aliphatic and / or alicyclic petroleum fractions, chlorinated hydrocarbons such as chloroform and trichloroethane, cyclic and acyclic ethers such as dioxane and tetrahydrofuran, Polyalkylene glycol dialkyl ethers such as propylene glycol dimethyl ether, esters of mono, di or polycarboxylic acids, phthalates or other plasticizers such as ethyl acetate, butyl acetate, butyrolactone, dimethyl 2-methyl glutarate, triacetin, dicarboxylic acids or polycarboxylic acid ester, referred to as "dibasic ester", dialkyl esters of C ₂ -C ₄ dicarboxylic acid, ethyl glycol acetate, alkyl glycol esters such as methoxypropyl acetate, methyl isobutyl Ke Emissions, cyclohexanone, ketones such as acetone, dimethylformamide, include acid amides such as N- methylpyrrolidone.

  The uretdione compound of the general formula (III) is obtained by reaction of Y—OH with a uretdione group-containing diisocyanate as described in EP1593700.

  Uretodione-containing diisocyanates are described, for example, in EP0795569. The preparation of these uretdione diisocyanates is described, for example, in DE 1670720, EP45995, EP99976, EP1174428 and the literature cited therein. The uretdione-containing diisocyanate is preferably 1,4-diisocyanatobutane, hexamethylene diisocyanate (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2 Dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4′- Diisocyanatodicyclohexylmethane, tolylene diisocyanate (TDI), 1-isocyanato-1-me 4 (3) isocyanatomethylcyclohexane, bisisocyanatomethylnorbornane, and 1,3- and 1,4-bis (2-isocyanatoprop-2-yl) benzene (TMXDI), or such diisocyanates It is a cyclic dimerization product of a mixture of nates. Particularly preferred uretdione-containing diisocyanates herein are the cyclic dimerization products of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and tolylene diisocyanate (TDI).

  In this connection, it is possible to use the catalysts or solvents presented for the synthesis of the isocyanate adduct (II), and the indicated temperature ranges can be applied.

Compounds of general formula (V) Suitable compounds of general formula (V) include, for example, dicarboxylic acids and anhydrides, acyl chlorides or esterifiable derivatives such as, for example, dialkyl esters such as dimethyl or diethyl esters. , Y-OH or diols and compounds prepared by reaction with monofunctional carboxylic acids. The formation of dihydroxy polyester can be suppressed if necessary by using the corresponding stoichiometric amount of monofunctional carboxylic acid. Esterification may be carried out in bulk or by azeotropic esterification in the presence of an azeotrope forming agent. This type of condensation reaction is carried out at a temperature of about 50 ° C to 250 ° C, for example.

  Examples of dicarboxylic acids that can be used accordingly are succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid, or dimerized fatty acids and their isomers, and their Hydrogenated product.

  Examples of diols that can be used accordingly are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cis-1 , 2-cyclohexanedimethanol, trans-1,2-cyclohexanedimethanol, and polyglycols based on ethylene glycol and / or propylene glycol.

  Monocarboxylic acids used accordingly as starting components preferably have 1 to 42, more particularly 4 to 18, more preferably 8 to 14 carbon atoms, saturated or unsaturated, aliphatic or aromatic May be linear, branched and / or cyclic.

  Examples of corresponding suitable monocarboxylic acids are stearic acid, isostearic acid, oleic acid, lauric acid and benzoic acid. Other suitable acids are tertiary saturated, also referred to as kofuic acid, such as 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, tert-nonanoic acid and neodecanoic acid. Monocarboxylic acid. As commercial products, this type of kofoic acid is also known, for example, under the name Versatic® acid (Momentive), Neo acid (Exxon) or CeKanoic acid (Kuhlmann). A suitable example is Momentive Versatic® acid 5, 6, 9, 10, 913, 1019.

  The compound of the general formula (V) is usually in the form of a polyester compound having at least 5, preferably 6 to 70 ester groups in each case. The ester group typically improves solubility.

  According to a particular embodiment of the invention, the compound of formula (V) also has an ether group.

  The compound of formula (V) preferably has exactly one carboxyl group in each case, and the compound of formula (V) preferably reacts with polyamine PA or modified polyamine PA in each case It does not contain other functional groups that react during

Often at least 50 wt.%, Preferably 70-100 wt.%, Of the compounds of the formula (V) used are present in the form of linear monocarboxy-functional polyesters, which are preferably in each case 500-10000. , Preferably having a number average molecular weight ( _Mn ) of 800-8000.

A number average molecular weight ( _Mn ) of less than 500 or greater than 10,000 often impairs general compatibility.

  Particularly suitable polyesters are propiolactones in the presence of one or more polycondensation of optionally substituted hydroxycarboxylic acids, such as ricinoleic acid or 12-hydroxystearic acid, and / or in the presence of monocarboxylic acids. , Valerolactone, caprolactone and the like can be obtained by ring-opening polymerization of the corresponding lactone. Lactone polymerization is carried out in a known manner, for example initiated by p-toluenesulfonic acid or dibutyltin dilaurate at a temperature of about 50 ° C. to 200 ° C. Particularly preferred are polyesters based on ε-caprolactone, optionally in combination with δ-valerolactone.

Compound of general formula (VI) The compound of general formula (VI) is a phosphate ester. These compounds are usefully prepared by reaction of at least one hydroxyl group, preferably Y-OH of exactly one hydroxyl group, with an ester-forming phosphorus compound. The compound of the formula (VI) preferably has in each case exactly one phosphate group, and the compound of the formula (VI) is preferably in each case of the reaction with the polyamine PA or the modified polyamine PA. There are no other functional groups that react with amine groups and / or hydroxyl groups in between.

  An ester forming phosphorus compound is understood to be a compound capable of forming a phosphate ester by reaction with a compound containing a hydroxyl group. Examples of ester-forming phosphorus compounds that can be used include polyphosphoric acid, phosphorus pentoxide, phosphorus oxychloride, and acetyl phosphate. It is preferable to use polyphosphoric acid or phosphorus pentoxide, more preferably polyphosphoric acid. Polyesters mainly form monoesters, and phosphorus pentoxide mainly forms monoester / diester mixtures. Monoesters are preferred. It is also possible to use a mixture of different components for phosphorylation in the phosphorylation reaction.

  The reaction of the ester-forming phosphorus compound and the hydroxyl compound Y-OH is preferably carried out at a temperature up to 150 ° C., preferably below 100 ° C., preferably without solvent. Alternatively, the reaction may be carried out in the presence of a suitable inert solvent (eg methoxypropyl acetate).

  Monofunctionality in the compounds of formulas (V) and (VI) is desirable to avoid cross-linking, which causes a decrease in solubility, poor compatibility, excessive viscosity, and / or excessively low compatibility. .

  The reaction of polyamine PA or modified polyamine PA with isocyanate adduct (II) is carried out under the conditions described for the preparation of compounds (II) and (III). The molar ratio of the isocyanate group of compound (II) to the reactive group of polyamine PA or modified polyamine PA is in the range of 0.1: 1 to 1: 1. In connection with this reaction, the reactive groups of polyamine PA or modified polyamine PA include primary and secondary amino groups and alcohol groups.

  The conditions applicable to the reaction of polyamine PA or modified polyamine PA with uretdione (III) are the same as specified for the preparation of compounds (II) and (III). In the preferred reaction regime, no catalyst is used and the temperature range is between room temperature and 100 ° C. The molar ratio of the uretdione group of compound (III) to the reactive group of polyamine PA or modified polyamine PA is in the range of 0.1: 1 to 1: 1. In connection with this reaction, the reactive groups of polyamine PA or modified polyamine PA include primary and secondary amino groups and alcohol groups.

  The Michael addition of acrylate (IV) is carried out in the presence of a solvent or in bulk in the temperature range from room temperature to 150 ° C, preferably 100 ° C, more preferably 70 ° C.

  The molar ratio of the acrylate group of compound (IV) to the reactive group of polyamine PA or modified polyamine PA is preferably 0.1: 1 to 1: 1. In connection with this reaction, the reactive groups of polyamine PA or modified polyamine PA are considered primary and secondary amino groups.

Reaction with compounds of general formula (V), (VI) and (VII) The reaction of compounds of general formula (V), (VI) and (VII) with polyamine PA or modified polyamine PA is carried out in the presence of a solvent. Under or in bulk, it is carried out in the temperature range from room temperature to 200 ° C, preferably 150 ° C, more preferably 120 ° C.

  In the case of reaction of polyamine PA or modified polyamine PA with a compound of formula (V), salt formation and / or amide formation is possible depending on the reaction regime. Salt formation occurs under mild reaction conditions between the acid groups in the compound of formula (V) and the nitrogen atoms of the primary, secondary, and tertiary amino groups of the polyamine. Amide formation is possible only in the case of primary and secondary amino groups and occurs by dehydration under more severe reaction conditions such as higher temperatures and / or longer reaction times than in the case of salt formation.

  Salt formation requires temperatures below 150 ° C, often temperatures of 120 ° C are used, and reactions at temperatures below 100 ° C are preferred. In contrast, amide formation proceeds by dehydration at temperatures of at least 100 ° C., often 150 ° C., or even temperatures up to 200 ° C. In these reactions, it is also possible to form a mixture of the chloride product and the amide.

  The reaction of polyamine PA or modified polyamine PA with compounds of formula (VI) and (VII) is carried out by salt formation.

  The reaction is useful in a weight ratio of polyamine to compounds of formula (V), (VI), and (VII) from 1: 500 to 1: 1, preferably from 1: 200 to 1: 5, more preferably 1: It is performed at 100 to 10: 1. Low proportions of polyamines often result in low levels of adsorption on solid surfaces, and high proportions of polyamines often represent difficulties in terms of poor solubility and ease of handling.

  In the presence of polyamine PA or modified polyamine PA, the lactone polymerization described under item (b) is catalyzed by, for example, p-toluenesulfonic acid or dibutyltin dilaurate at a temperature of about 50 ° C. to 200 ° C. Carried out under the conditions mentioned for the production of polyester Y-OH. Particularly preferred are polyesters based on ε-caprolactone, optionally in combination with δ-valerolactone.

  Depending on the field of application, the solvent used in the synthesis may remain in the reaction mixture or may be wholly or partly removed and optionally replaced by other solvents or carrier media. The solvent is removed, in whole or in part, for example by distillation, optionally under reduced pressure and / or azeotropically with the addition of water. The active substance can optionally be isolated by precipitation, by the addition of a non-solvent such as an aliphatic hydrocarbon such as hexane, and subsequent removal by filtration, optionally dried. The active substance obtained by one of these methods can then be diluted in a solvent suitable for the particular field of use, or optionally used in pure form, for example in the case of powder coating Can be applied to an inert carrier. For applications where the use of solids is preferred, such as powder coating or certain plastic processing methods, the compounds are also converted to solid forms by other known methods.

Examples of such methods, microencapsulation, spray drying, there is adsorption onto a solid support such as SiO _2, or PGSS process (Particles from Gas saturated solution).

  The polymers of the present invention may be partially or wholly salified with an acid. Examples of acids are carboxylic acids, phosphoric acids, polyethers, polyesters or phosphate esters of polyether-polyester block copolymers, and sulfonic acids.

  Furthermore, the tertiary amines of the compounds of the present invention can be obtained by alkyl halides such as benzyl chloride, methyl iodide or oxiranes such as alkylenes in the presence of acids such as carboxylic acids or phosphoric acids and their esters. It may be converted to the corresponding quaternary ammonium salt by an alkylation reaction with oxide or glycidyl ether.

  The hydroxyl group optionally present in the polymer of the present invention may further react with an ester-forming phosphorus compound such as polyphosphoric acid to form a phosphate ester.

  Tertiary amines can be converted to amine oxides with oxygen, peroxo compounds such as percarboxylic acids, and hydrogen peroxide, which can then be further salified with acids such as hydrochloric acid.

  The present invention is a dispersion comprising a medium to be dispersed as well as a particulate solid to be dispersed, and is 0.1 to 10 wt%, preferably 0.3 to 4.5 wt% of the present invention relative to the total weight of the dispersion. It also relates to dispersions in which the polymer PAS is used as wetting and dispersing agent, the dispersion preferably being in the form of an inorganic filler and / or in the form of an organic or inorganic pigment and / or carbon. It exists in the form of nanotubes and / or in the form of graphene.

  The dispersion according to the invention is preferably in the form of a liquid ink or coating material, in particular a paint or varnish.

  The present invention further relates to a particle preparation comprising 30.0-99.9 wt% particulate solid and 0.1-70.0 wt% polymer PAS of the present invention.

  Finally, the invention relates to the use of the inventive polymer PAS as wetting and dispersing agents.

  The polymer PAS of the present invention can be used, for example, in the manufacture or processing of paints and varnishes, printing inks, paper coatings, leather and fiber dyes, pastes, pigment concentrates, ceramics, cosmetic products, and in particular these products In the case of including solids such as pigments and / or fillers, they are particularly used in the known field of using dispersants.

  The polymer PAS of the present invention is a synthetic, semi-synthetic or natural polymer material such as polyvinyl chloride, saturated or unsaturated polyester, polyurethane, polystyrene, polyacrylate, polyamide, epoxy resin, polyolefin such as polyethylene or polypropylene. It can also be used for the production or processing of base casting compounds and / or molding compounds. For example, casting compounds, PVC plastisols, gel coats, polymer concrete, printed circuit boards, industrial paints, wood and furniture varnishes, vehicle finishes, marine paints, anticorrosion paints, can paints and / or coil paints, decorating paints, and Corresponding polymers for producing building paints can be used. Examples of conventional binders are resins based on polyurethane, cellulose nitrate, cellulose acetobutyrate, alkyd, melamine, polyester, chlorinated rubber, epoxide, and acrylate. Examples of aqueous coatings are, for example, cationic or anionic electrodeposition coating systems for automobile bodies. Other examples are undercoats, silicate paints, emulsion paints, water-based alkyd-based paints, alkyd emulsions, hybrid systems, two-component systems, polyurethane dispersions, and acrylate dispersions.

  The polymer PAS of the present invention is also particularly suitable as a dispersant for producing solid concentrates such as pigment concentrates. For this purpose, for example, the polymer PAS is introduced into a carrier medium such as an organic solvent, a plasticizer and / or water, and the solid for dispersion is added with stirring. These concentrates may further contain binders and / or other auxiliaries. However, with the polymer PAS according to the invention, it is possible in particular to produce pigment concentrates which are stable and free of binders. With the polymer it is also possible to produce a flowable solid concentrate from a pigment presscake. In this case, the polymer according to the invention is mixed with the press cake, which still contains organic solvents, plasticizers and / or water and can disperse the resulting mixture. The solid concentrate produced by various methods can then be incorporated into various substrates such as, for example, alkyd resins, polyester resins, acrylate resins, polyurethane resins, or epoxy resins. However, pigments can be dispersed directly in the polymer PAS of the present invention without solvent and as a result are particularly suitable for coloring thermoplastic and thermosetting plastic formulations.

  The polymer PAS of the present invention can also be advantageously used in the production of inks for “non-impact” printing methods, such as “thermal ink jet” and “bubble jet® method”. These inks may be, for example, aqueous ink formulations, solvent-based ink formulations, solventless or low solvent inks for UV applications, and wax-like inks.

  The polymer PAS of the present invention is also advantageous for the production of displays based on color filters for liquid crystal displays, liquid crystal screens, color separation devices, sensors, plasma screens, SEDs (surface conduction electron emission displays) and MLCCs (multilayer ceramic compounds). Can be used for In this case, the liquid color filter varnish (also called color resist) is applied by any wide range of application methods such as spin coating, knife coating, a combination of the two, or by “non-impact” printing methods such as, for example, ink jet methods. be able to. MLCC technology is used in the manufacture of microchips and printed circuit boards.

  The polymer PAS of the present invention can also be used to produce cosmetic products such as makeup cosmetics, powder cosmetics, lipsticks, hair colorants, creams, nail varnishes, and sunscreen cosmetics. These products may be present in customary states such as, for example, W / O or O / W emulsions, solutions, gels, creams, lotions or sprays. The polymers according to the invention can advantageously be used in dispersions used to produce these products. These dispersions are carrier media customary for cosmetics for these purposes such as water, castor oil or silicone oil, and solids, examples being organic and inorganic pigments such as titanium dioxide or iron oxide The carrier medium may be included.

  Finally, this type of dispersant can also be used to produce a colored coating on a substrate, in which case the colored paint is applied to the substrate and the colored paint applied to the substrate is Fired, cured, or crosslinked.

  The polymer PAS of the present invention can be used alone or in combination with customary binders. When used for polyolefins, it may be advantageous, for example, to use the corresponding low molecular weight polyolefins with PAS as carrier materials.

  Another possible use of the polymer PAS of the invention is in the manufacture of dispersible solids in the form of powder and / or fiber particles, more particularly dispersible pigments or polymer fillers, in which case the particles Are coated with PAS. Such coatings of organic and inorganic solids are performed in a known manner. In this case, the solvent or emulsion medium may be removed or left in the mixture to form a paste. These pastes are customary commercial products and may additionally contain a binder fraction and further auxiliaries and auxiliaries. In particular, in the case of pigments, coating of the pigment surface may be carried out during or after pigment synthesis or during or after pigment conditioning, for example by addition of PAS to the pigment suspension. Pigments that have been pretreated in this way are notable for their outstanding ease of incorporation and improved viscosity, flocculation and gloss properties, and stronger color strength compared to untreated pigments.

  Examples of pigments are mono, di, tri and polyazo pigments, oxazine, dioxazine, and thiazine pigments, diketopyrrolopyrrole, phthalocyanine, ultramarine, and other metal complex pigments, indigoid pigments, diphenylmethane, triarylmethane, xanthene, acridine Quinacridone, methine pigments, anthraquinones, pyranthrones, perylenes and other polycyclic carbonyl pigments. Other examples of organic pigments include the following research paper: Herbst, K.M. Hunger “Industrial Organic Pigments”, 1997 (Publisher: Wiley-VCH, ISBN: 3-527-28836-8). Examples of inorganic pigments are carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithopone, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, zinc acid Based on cobalt, antimony oxide, antimony sulfide, chromium oxide, zinc chromate based pigments, nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum Mixed metal oxide (example: nickel titanium yellow, bismuth vanadate / bismuth molybdate yellow, or chrome titanium yellow). Another example is the following research paper: Buxbaum, “Industrial Inorganic Pigments”, 1998 (Publisher: Wiley-VCH, ISBN: 3-527-28878-3). Inorganic pigments are also magnetic pigments based on pure iron, iron oxide and chromium oxide or mixed oxides, metallic effect pigments made of aluminum, zinc, copper or brass, and pearlescent pigments, fluorescent and phosphorescent fluorescent It may be a pigment.

  Other examples are nanoscale organic or inorganic solids having a particle size of less than 100 nm, such as certain types of carbon black, or particles made of metal and metalloid oxides and / or hydroxides, and mixed metals And / or particles of mixed metalloid oxides and / or hydroxides. For example, oxides such as aluminum, silicon, zinc, titanium and / or oxide hydroxides can be used to produce this type of very finely divided solid. The methods for producing these oxide and / or hydroxide and / or oxide hydroxide particles are, for example, ion exchange operations, plasma operations, sol-gel processes, precipitation, grinding (eg by grinding) or It can be carried out by any of a wide variety of methods such as flame hydrolysis. These nanoscale solids may also be called hybrid particles consisting of an inorganic core and an organic shell (or vice versa).

  Examples of fillers in powder or fiber form are, for example, aluminum oxide, aluminum hydroxide, silicon dioxide, key slagger, siliceous earth, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, finely ground slate , Calcium sulfate, barium sulfate, calcium carbonate, calcite, dolomite, glass, polyvinylidene fluoride (PVDF), or particles in the form of carbon powder or fibers. Other examples of pigments or fillers are found, for example, in EP-A-0270126. Similarly, flame retardants such as aluminum hydroxide or magnesium hydroxide and matting agents such as silica are equally susceptible to effective dispersion and stabilization.

  The polymer PAS of the present invention can also be used as an emulsifier, phase mediator (liquid / liquid compatibilizer) or adhesion promoter.

  The invention is explained in more detail below by means of examples.

  In the following, the present invention will be described using examples. Except where indicated otherwise, numerical values in parts are parts by weight and numerical values in percent are percentages by weight.

Method of measurement In the case of molecularly heterogeneous substances, the reported molecular weight represents the average of the number averages, as in the description above. The molecular weight or number average molecular weight (M _n ) is the titration OH number, NCO number, amine number, and acid number, respectively, in the presence of determinable functional end groups such as hydroxyl, NCO, amino, or acid groups. By determining the end group. For compounds for which end group determination is not applicable, the number average molecular weight is measured against a polystyrene standard using gel permeation chromatography.

Solid content Sample (2.0 ± 0.1 g of material under test) is weighed into a pre-dried aluminum pan, dried in a drying cabinet at 150 ° C. for 10 minutes, cooled in a desiccator, and then again Weigh. The residue corresponds to the solid fraction.

OH number The alcoholic hydroxyl group is reacted by acetylation with excess acetic anhydride. The excess acetic anhydride is then cleaved by the addition of water to obtain acetic acid and back titration is performed using ethanolic KOH. The OH number indicates the amount of KOH equivalent to the amount of acetic acid bound by acetylation of 1 g of substance.

Acid number Acid number (AN) represents the amount of mg of KOH required to neutralize 1 g of material under defined conditions. The acid value is measured according to DIN EN ISO 2114 by a neutralization reaction with 0.1 N KOH in ethanol as a titrant.

Amine number The amine number (AmN) represents the mg amount of KOH corresponding to the amine fraction of 1 g of material. The amine number is measured according to DIN 16945 by a neutralization reaction with 0.1N perchloric acid in acetic acid as titrant.
R—NH ₂ + HClO ₄ → R—NH ₃ ⁺ + ClO ₄ ⁻

  The addition of inert solvents such as cyclohexane, dioxane, chlorobenzene, acetone, and methyl ethyl ketone can improve the titration of very weak bases.

NCO value The free NCO content of the polyisocyanate used, and the course of the NCO addition reaction, are determined according to EN ISO 9369 by reaction with butylamine followed by titration with an excess of amine. These methods are also described in Saul Patai “The Chemistry of Cyanates and the Thior Derivatives”, Part 1, Chapter 5, 1977.

Gel permeation chromatography (GPC)
Gel permeation chromatography was performed at 40 ° C. with a high pressure liquid chromatography pump (Bischoff HPLC 2200) and a refractive index detector (Waters 419). The eluent used was tetrahydrofuran and the elution rate was 1 ml / min. Calibration was performed using polystyrene standards. Number average molecular weight (M _n ), weight average molecular weight (M _w ), and polymolecular index PMI = M _w / M _n were calculated using the NTeqGPC program.

General Manufacturing Protocol for Polyamine PA in Synthesis Option 1 General Manufacturing Protocol (Option 1, Method a)
A four-necked flask equipped with a water separator, a stirrer, a thermometer, and a nitrogen inlet tube is charged with a specified amount of amine A. Cool in a water bath and meter in a specified amount of water at a temperature below 80 ° C. while stirring. After cooling to room temperature, a specified amount of acrylate is metered in at a temperature below 50 ° C. The reaction vessel is optionally cooled with a water bath. The reaction is monitored by 1H-NMR. When all double bonds have undergone the reaction, the temperature is raised to 80 ° C. and the reaction mixture is stirred at 80 ° C. for about 3 hours. Thereafter, the alcohol formed and the water used as solvent are removed at 80 ° C. and 20 mbar. This produces more alcohol and removes it. The reaction is monitored by IR spectroscopy. As soon as the IR spectrum shows full conversion of the ester, the reaction is considered to be the end point.

General manufacturing protocol (option 1, method b)
A four-necked flask equipped with a water separator, a stirrer, a thermometer, and a nitrogen inlet tube is charged with a specified amount of amine A. When a defined amount of ethanol is added with stirring, the temperature rises somewhat. After cooling to room temperature, a specified amount of acrylate is metered in at a temperature below 50 ° C. The reaction vessel is optionally cooled with a water bath. The reaction is monitored by 1H-NMR. When all double bonds have undergone the reaction, the temperature is raised to 80 ° C. and the reaction mixture is stirred at 80 ° C. and 500 mbar for about 3 hours. Thereafter, the temperature is continuously increased to 145 ° C. and the pressure is decreased to 300 mbar. The ethanol used as solvent and the alcohol formed are removed from the reaction mixture. The reaction is monitored by IR spectroscopy. As soon as the IR spectrum shows full conversion of the ester, the reaction is considered to be the end point.

General manufacturing protocol (option 1, method c)
A four-necked flask equipped with a water separator, a stirrer, a thermometer, and a nitrogen inlet tube is charged with a specified amount of amine A. While stirring, a specified amount of acrylate is added at a temperature below 50 ° C. The reaction vessel is optionally cooled with a water bath. The reaction is monitored by 1H-NMR. When all double bonds have undergone the reaction, the temperature is raised to 100 ° C. and the reaction mixture is stirred at 100 ° C. for about 2 hours. Thereafter, the temperature is increased to 130 ° C. and the pressure is decreased to 300 mbar. The alcohol formed is removed from the reaction mixture. The reaction is monitored by IR spectroscopy. As soon as the IR spectrum shows full conversion of the ester, the reaction is considered to be the end point.

Option 1-Production example PA23 ^*
Step 1
A four-necked flask equipped with a water separator, stirrer, thermometer, and nitrogen inlet tube is charged with 44.1 parts of diethanolamine (amine A) together with 15.9 parts of ethanol and this is the starting charge. Homogenize things. Then 40.0 parts of ethyl acrylate with a temperature of 35-40 ° C. are metered in. The reaction is monitored by 1H-NMR. If all double bonds have undergone the reaction, at 60 ° C., the pressure is continuously reduced from 500 mbar to 200 mbar to remove the ethanol from the reaction mixture. This “CG _h building block” can be subjected to polycondensation immediately after its manufacture or stored for later use.

Step 2
A four-necked flask equipped with a water separator, stirrer, thermometer, and nitrogen inlet tube was charged with 6.71 g of 1,1,1-trimethylolpropane, and the starting charge was stirred while 135 Heat to ° C. Using a dropping funnel, 31.57 g of CG _h building block is added dropwise with 0.039 g of tetrabutyl titanate and the ethanol formed is removed by distillation. If no further formation of ethanol can be observed, an additional 73.68 g of CG _h building block is added along with 0.074 g of tetrabutyl titanate. The reaction mixture is heated to 140 ° C. and stirred until further formation of ethanol can no longer be observed. If no further formation of ethanol can be observed, the reaction is considered endpoint.
^* Not listed in Table 1.

  The preparation of the uretdione-containing intermediate of the general formula (III) (ie the reaction product between the uretdione-containing polyisocyanate and the compound of the formula Y-OH) is carried out as described, for example, in DE 102004022753.

Preparation of uretdione compounds of the general formula (III) The preparation of hydroxyl-functional lactone polyesters is carried out, for example, as described in EP 158678.

Preparation of polyester 1 (OH number: 47 mg KOH / g) In a four-necked flask equipped with a reflux condenser, stirrer, thermometer, nitrogen inlet tube, 20.3 parts hexadecanol and 79.7 parts ε -Homogenize caprolactone, mix with 200 ppm dibutyltin dilaurate and heat to 170 ° C. The mixture is stirred at this temperature until the solids content exceeds 97%. The resulting polyester has an OH number of 47 mg KOH / g.

  The production of polyesters 2-6 is carried out as described in the production of polyester 1. The produced polyesters are listed in the table below.

General production protocol for uretdione intermediates of general formula (III) In a four-necked flask equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, a defined amount of polyisocyanate is converted into individual intermediates. Mix with the prescribed amount of ingredients reported against. The mixture is then heated to 80 ° C., 200 ppm of dibutyltin dilaurate is added and the mixture is stirred at 80 ° C. until the NCO content drops below 0.1%.

General manufacturing protocol for the preparation examples listed in the table below General manufacturing protocol for the reaction of polyamines with uretdione intermediates of general formula (III) Reflux condenser, stirrer, thermometer and nitrogen inlet tube A four-necked flask equipped is charged with a defined amount of polyamine and the starting charge is heated to 90 ° C. As soon as this temperature is reached, a defined amount of uretdione intermediate is added. Depending on the viscosity, the intermediate is heated during the addition. The reaction can be somewhat exothermic, but does not need to be cooled and the dissipated energy is utilized to facilitate the reaction. The reaction mixture is stirred at spontaneous temperature for 2 hours.

General manufacturing protocol for further reaction with component 2 Component 2 = Epoxide A specified amount of epoxide is added to the reaction mixture in one portion and the mixture is heated to 140 ° C. The batch may be monitored at this temperature, for example by NMR measurements, but is stirred until the epoxide is completely reacted.

Component 2 = Acrylate A specified amount of acrylate is added to the reaction mixture in one portion at 80 ° C. The reaction mixture may be similarly monitored at this temperature, for example by NMR measurements, but is stirred until the acrylate has completely reacted.

Component 2 = Mono adduct A defined amount of mono adduct is metered into the reaction mixture at 80 ° C. using a dropping funnel. The reaction mixture is stirred at this temperature for 3 hours.

PAS12
A defined amount of P acid 1 is slowly metered into the reaction mixture at 80 ° C. using a dropping funnel. The reaction mixture is subsequently stirred at 100 ° C. for 2 hours.

PAS15
A specified amount of C acid 1 is slowly metered into the reaction mixture at 80 ° C. using a dropping funnel. The reaction mixture is subsequently stirred at 100 ° C. for 2 hours.

An asterisk “ ^* ” represents a comparative example that is not the present invention.
CMP: = comparative acrylate not according to the invention 1: = 2-ethylhexyl acrylate acrylate 2: = polypropylene glycol monoacrylate, Blemmer AP 400, Sartomer
Acrylate 3: = n-butyl acrylate epoxide 1: = 2-ethylhexyl glycidyl ether epoxide 2: = n-butyl glycid ether PEI 1200: = polyethyleneimine, Epomin SP012, Nippon Shokubai Co., Ltd. PMA: = 1- Methoxy-2-propyl acetate C acid 1: = tall oil fatty acid, AN: 195 mg KOH / g
P acid 1: = phosphorylated, isotridecanol-initiated polyethylene glycol, AN: 105 mg KOH / g
Monoadduct M2: = reaction product of polyether 2 with Desmodur T 100 (see Table 7)

General manufacturing protocol for the manufacturing examples listed in the table below. A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, together with a specified amount of polyamine and a specified amount of ε- Charge caprolactone and 200 ppm dibutyltin dilaurate and heat the starting charge to 170 ° C. with stirring and stir at this temperature until a solids content of 98% is reached.

General production protocol for the production examples listed in the table below Reaction with epoxide components A four-necked flask equipped with stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a specified amount of polyamine. And heated to 100 ° C. While stirring, the specified amount of epoxide component is slowly metered in, during which the reaction temperature should not exceed 120 ° C. This is followed by stirring at 120 ° C. until conversion of the epoxide component is complete. The progress of the reaction may be monitored, for example, by NMR measurement.

Reaction with the acrylate component The reaction of the polyamide already reacted with the epoxide component is carried out in the same manner as the reaction of the pure polyamine with the acrylate component. A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a specified amount of polyamine and heated to 60 ° C. The specified amount of acrylate component is slowly metered in, during which the reaction temperature should not exceed 90 ° C. This is followed by stirring at 80 ° C. until conversion of the acrylate component is complete. The progress of the reaction may be monitored by NMR measurement.

  When the polyamine is reacted with the epoxide component and the acrylate component, the reaction with the epoxide is preferably carried out first.

General manufacturing protocol for isocyanate adducts of general formula (II) Into a four-necked flask equipped with stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, 33.4 g of Desmodur T 100 (TDI 100, NCO content = 48.8 wt%) and 0.57 g of benzoyl chloride and thoroughly mix these ingredients. A specified amount of alcohol component (which does not contain water and in the case of polyethers does not contain alkali) is slowly metered in and the temperature is 55 ° C. or lower. Following the metered addition, the mixture is stirred at 55 ° C. for a further 3 hours. Excess TDI is removed from the reaction mixture at 150 ° C. using a thin film evaporator.

General production protocol for the production examples listed in the table below Reaction with epoxide components A four-necked flask equipped with stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a specified amount of polyamine. And is heated to 100 ° C. While stirring, the specified amount of epoxide component is slowly metered in, during which the reaction temperature should not exceed 120 ° C. This is followed by stirring at 120 ° C. until epoxide component conversion is complete. The progress of the reaction may be monitored, for example, by NMR measurement.

Reaction with acrylate component A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a defined amount of polyamine and heated to 60 ° C. The specified amount of acrylate component is slowly metered in, during which the reaction temperature should not exceed 100 ° C. This is followed by stirring at 80 ° C. until conversion of the acrylate component is complete. The progress of the reaction may be monitored by NMR measurement.

Reaction with Glycerin Carbonate A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a specified amount of polyamine and heated to 80 ° C. Slowly meter in a specified amount of glycerin carbonate. This is followed by stirring at 80 ° C. until the conversion of glycerin carbonate is complete. The progress of the reaction may be monitored by NMR measurement.

Reaction with ε-caprolactone A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a specified amount of polyamine and heated to 80 ° C. Add the specified amount of ε-caprolactone. This is followed by stirring at 80 ° C. for 2 hours.

Reaction with monoadducts The hydroxyl groups as well as the amino groups produced by component 1 or already present in the polyamine PA will be reacted with the isocyanate adducts (monoadducts) of the general formula (II) The reaction is carried out with the production protocol corresponding to the reaction of the polyamide with no hydroxyl groups and the monoadduct (component 2), with the addition of 200 ppm of dibutyltin dilaurate.

  A four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube is charged with a defined amount of polyamine and the initial charge is heated to 50 ° C. A specified amount of monoadduct is metered in slowly at a reaction temperature of 55 ° C. or lower. The reaction mixture is subsequently stirred at 70 ° C. for a further 2 hours.

General manufacturing protocol for the reaction of amine A with polyfunctional acrylates and / or epoxides to obtain polyamine PA of option 3 General manufacturing protocol (option 3, method a)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube is charged with amine A R1a) as indicated and optionally listed solvent (LM) as indicated. Under N ₂ gas, the reaction components R1b) and R1c) are slowly metered in with stirring, during which the reaction temperature should not exceed 100 ° C. This is followed by a 2 hour post-reaction at 100 ° C.

General manufacturing protocol (option 3, method b)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with amine A R1a), as indicated, and the solvents (LM) listed as needed, at the start Heat the filling to 100 ° C. Under N ₂ gas, the reaction components R1b) and R1c) are slowly metered in with stirring, during which the reaction temperature should not exceed 120 ° C. This is followed by a 1 hour post-reaction at 110 ° C.

Reaction production example PAS45 of polyamine PA and uretdione-containing component S of general formula (III)
A reaction vessel equipped with a reflux condenser and stirrer is charged with 150 g of uretdione-containing precursor I13 and the starting charge is heated to 90 ° C. As soon as this temperature is reached, 84.3 g of polyamine PA28 are added. The reaction mixture is then stirred at 100 ° C. for a further hour.

Production example PAS46
A reaction vessel equipped with a reflux condenser and stirrer is charged with 100 g of uretdione-containing precursor I13, and the starting charge is heated to 90 ° C. As soon as this temperature is reached, 92.7 g of polyamine PA33 is added. The reaction mixture is then stirred at 100 ° C. for a further hour.

Comparative Example CMP3 ^*
A reaction vessel equipped with a reflux condenser and stirrer is charged with 150 g of uretdione-containing precursor I13 and the starting charge is heated to 90 ° C. As soon as this temperature is reached, 84.3 g of PEI 1200 is added. The reaction mixture is then stirred at 100 ° C. for a further hour.
^* It is not the present invention

Reaction example PAS47 of polyamine PA and monocarboxyl functional polyester of general formula (V)
In a reaction vessel equipped with a reflux condenser and stirrer, a mixture of 100 g of lauric acid-initiated ε-caprolactone polyester having an acid number of 28 mg KOH / g was heated to 120 ° C. with 32 g of polyamine PA28, and the mixture was Stir at temperature for 3 hours. The resulting product is solid and waxy at room temperature.

Reaction example PAS48 of polyamine PA and phosphate ester of general formula (VI)
In a reaction vessel equipped with a reflux condenser and a stirrer, 92.5 g of a mixture of polyester 3 are heated with 7.5 g of polyphosphoric acid to 90 ° C. and the mixture is stirred at this temperature for 3 hours. 28 g of polyamine PA30 are added, followed by stirring at 100 ° C. for a further hour. The resulting product is solid and waxy at room temperature.

Production example PAS49
In a reaction vessel equipped with a reflux condenser and stirrer, 90 g of the polyester 4 mixture are heated to 90 ° C. with 10 g of polyphosphoric acid and the mixture is stirred at this temperature for 3 hours. 45 g of polyamine PA25 are added, followed by stirring at 100 ° C. for a further hour.

Performance Test Use of the inventive polymers as wetting and dispersing agents for the preparation of pigment concentrates and their use in paint systems Uralac SN-804 S2-65 ND: polyester resin, manufacturer DSM resin Cymel 303 : Melamine-formaldehyde resin, manufacturer Cytec Industries
Dynapol Catalyst 1203: “Blocked” sulfonic acid catalyst, manufacturer Evonik
Ti-Pure R960: Titanium dioxide pigment, manufacturer Du Pont
Aerosil R972: Hydrophobic fumed silica, manufacturer Degussa
Special Schwartz 4: Carbon black pigment, manufacturer Evonik
Heliogen Blau L 7101 F: Blue pigment, manufacturer BASF
Solvesso 150 ND: Aromatic solvent, manufacturer ExxonMobil
Dowanol PMA: 1-methoxy-2-propyl acetate, manufacturer Dow Chemical
Dowanol DPM: Dipropylene glycol monomethyl ether, manufacturer Dow Chemical
DBE: "Dibasic ester", manufacturer Du Pont
Disperbyk 170: Wetting and dispersing agent, manufacturer BYK-Chemie

Operation method Manufacture of paint Ti-Pure R960
Grinding conditions Dispermat CV, Teflon (registered trademark) disk, Φ4 cm, 20 min, 40 ° C., 8000 rpm (18.8 m / s)
Millbase to glass bead (1 mm diameter) ratio: 1: 1 (parts by weight)

Special Schwarz 4
Grinding conditions Dispermat CV, Teflon (registered trademark) disk, Φ4 cm, 60 min, 40 ° C., 10000 rpm
Millbase to glass bead (1 mm diameter) ratio: 1: 1 (parts by weight)

Heliogen Blau L 7101 F
Grinding conditions Dispermat CV, Teflon (registered trademark) disk, Φ4 cm, 40 minutes, 40 ° C., 10000 rpm
Millbase to glass bead (1 mm diameter) ratio: 1: 1 (parts by weight)

Production of test compound

  The viscosity of the test formulation was adjusted to 90-120 sec (DIN 4 flow cup, 23 ° C.) using Solvesso 150 ND after its manufacture. A portion of the test formulation was scored at 50 ° C. for 1 week.

Application of test formulation After overnight storage, the test formulation is subjected to the following conditions:
Support: Alcan aluminum sheet pre-coated with about 5 μm PU primer coat Doctor blade Application: 80 μm (when wet)
Oven temperature: 320 ° C
Firing time: 30s
Maximum metal temperature: 235 ° C
Dry film thickness: 18-20 μm
Applied to the support.

The float color, float mottle, and flocculation characteristics were evaluated as follows.
Each test formulation was divided into two parts.
The first portion of each test formulation was stirred with a toothed disk for 1 minute at 6000 revolutions per minute and then immediately applied to the right half of the support surface. At the same time, a second portion of each test formulation was applied to the left half of the support surface without prior agitation.

Abrasion Test Immediately after application, the newly applied paint film on both halves of the support surface was subjected to an abrasion test. For this purpose, several areas of the new paint film after application are subjected to mechanical friction, and then the color change caused by friction (abrasion effect) is compared with paint that has not been subjected to friction. It was measured. Causes of wear effects include, for example, pigment flocculation and / or floating mottle. If pigment flocs are present, they are disrupted by shear during wear, resulting in the original target color. The wear effect can be minimized by using a suitable dispersant and is therefore a measure of the effectiveness of the dispersant.

Colorimetric measurement Measuring instrument: color guide, BYK-Gardner
Light source: Standard light D65 (daylight)
Measurement field of view: 10 °
Measurement geometry: d / 8 ° spin (diffuse light, observation angle 8 °)
Number of measurements: n = 3

The colorimetric results are reproduced in the table below.
The ΔE value obtained for the formulation reports the color difference between the wear and non-wear areas of the coating (wear effect).
ΔE1 = ΔE non-stirring ΔE2 = ΔE stirring ΔE3 = ΔE non-stirring / stirring

What is compared to each other is PAS23 and PAS24 and non-inventive comparative example CMP2 ^* , while PAS4 is for non-inventive comparative example CMP1 ^* . This subdivision is triggered based on the structural similarity between PAS23 and PAS24 and CMP2 ^* and the structural similarity between PAS4 and CMP1 ^* .

Starting material Uralac SN-804 S2-65 ND: Polyester resin, manufacturer DSM Resins
Cymel 303: Melamine-formaldehyde resin, manufacturer Cytec Industries
Cycat 600: “Blocked” acid catalyst, manufacturer Cytec Industries
Ti-Pure R960: Titanium dioxide pigment, manufacturer Du Pont
Aerosil R972: Hydrophobic fumed silica, manufacturer Degussa
Solvesso 150 ND: Aromatic solvent, manufacturer ExxonMobil
Dowanol PMA: 1-methoxy-2-propyl acetate, manufacturer Dow Chemical
Dowanol DPM: Dipropylene glycol monomethyl ether, manufacturer Dow Chemical
Disperbyk 170: Wetting and dispersing agents, manufacturer BYK-Chemie

Operation method Manufacture of paint Ti-Pure R960
Grinding conditions Dispermat CV, Teflon (registered trademark) disk, Φ4 cm, 20 min, 40 ° C., 8000 rpm (18.8 m / s)
Millbase to glass bead (1 mm diameter) ratio: 1: 1 (parts by weight)

Paint composition

Additive metering and incorporation Following the addition of the catalyst, the additive was added. First, 0.45 g of additive was stirred using a spatula and then taken in using Dispermat CV, toothed disk, Φ4 cm, 3 min, 40 ° C., 1865 rpm (3 m / s).

Application of test formulation After production, the viscosity of the test formulation was adjusted to 90-120 sec using Solvesso 150 ND (DIN 4 flow cup, 23 ° C). The test formulation was applied to the support under overnight conditions following overnight storage.
Support: Alcan aluminum sheet pre-coated with about 5 μm PU primer coat Doctor blade Application: 80 μm (when wet)
Oven temperature: 320 ° C
Maximum metal temperature: 232 ° C
Firing time: 45s
Dry film thickness: 20 μm

  After firing, the sheet was cooled in water.

The test formulation was applied to a tinplate sheet in order to examine the clement hardness.
Support: Kruppel tin plate sheet E1
Doctor blade application: 80μm (when wet)
Oven temperature: 273 ° C
Maximum metal temperature: 232 ° C
Firing time: 30s
Dry film thickness: 20 μm

  After firing, the sheet was cooled in water.

Colorimetric measurement Instrument: Color Guide, BYK-Gardner
Light source: Standard light D65 (daylight)
Measurement field of view: 10 °
Measurement geometry: d / 8 ° spin (diffuse light, observation angle 8 °)
Number of measurements: n = 3

Paint cross-linking test For paint cross-linking test, a hammer (1 kg) was immersed in methyl ethyl ketone. Immediately after the immersion, the hammer was rubbed back and forth over the surface until the surface was broken. Results are expressed as reciprocating friction. The reported numbers indicate the number of reciprocating frictions that were made before the surface was destroyed.

Glossiness measurement Instrument: Micro-TRI-Gross, BYK Gardner
Angle: 60 °
Number of measurements: n = 3

Determination of clay hardness The purpose of this test is to evaluate the scratch resistance of the paint surface. This is done using a metal pin with a 1 mm diameter hemispherical ball that produces an adjustable load of 0-20 newton and a 30 mm cut. Next, the degree of penetration or destruction of the paint surface is confirmed.
Measuring instrument: Clenen apparatus, Type: Multitester 74
Test tip: Circular tip Result: The result is reported in newton (N).
Clement hardness: The reported value represents the load at which the surface is not destroyed.

  The results of the paint properties examined are reproduced in the table below.

As can be seen from the table, the paints according to the examples of the present invention exhibit lower yellowing and higher whiteness.
In the MEK test according to an embodiment of the present invention, a greater number of reciprocating frictions were required to break the surface. This suggests better crosslinking of the paint film compared to the non-inventive examples. Thus, in acid-catalyzed calcination systems, the examples of the present invention show clear advantages over polyethyleneimine based additives.

  For further evaluation of the compounds according to the invention, pigment concentrates were additionally produced based on the grind resin Laropal A81 (aldehyde resin, BASF). The numbers in the following formula are in grams.

  To produce a pigment paste, the raw materials shown in the table below are mixed with the same amount of 2 mm glass beads, continuously metered into a 500 ml Dispermat pot, and then using a 40 mm Teflon disc. Disperse at 40 ° C. Dispersion time for Kronos 2360 titanium dioxide was 8000 rpm for 30 minutes, Bayferrox 130M iron oxide for 40 minutes at 8000 rpm, Heliogen Blue L7101F for 40 minutes at 10,000 rpm, and Spezial Schwartz 4 carbon black for 10,000 rpm 60 minutes. The dispersed paste is sieved through a paper sieve (mesh size 80 μm) and supplied in a glass bottle.

Paste starting material Laropal A 81: Aldehyde resin, manufacturer BASF
Dowanol PMA: 1-methoxy-2-propyl acetate, manufacturer Dow Chemical
BYK-Synergist 2100: Pigment synergist, manufacturer BYK-Chemie
Aerosil R 972: Hydrophobic fumed silica, manufacturer Evonik
Bayferrox 130 M: red pigment, manufacturer Bayer
Heliogen Blau L 7101 F: Blue pigment, manufacturer BASF
Special Schwartz 4: Carbon black pigment, manufacturer Evonik
Kronos 2360: Titanium dioxide pigment, manufacturer Kronos

  A wear test was performed to evaluate flocculation stability. For this purpose, the paint is poured onto a PE film with an inclination angle of about 80 ° and the painted film is allowed to evaporate until just before the initial drying, at which point about 1/3 of the painted area. Wear with your finger until the color is constant. After the film is cured, the color difference between both the worn and non-rubbed areas is measured as the ΔE value. The smaller the ΔE value, the better the pigment stabilization with respect to flocculation and separation phenomena.

Transparent varnish starting material Setalux 1756 VV-65: acrylate resin, 65% strength in solvent naphtha, manufacturer Nuplex
Setamine US 138 BB-70: 70% strength melamine resin in n-butanol, manufacturer Nuplex
Shellsol A: Aromatic solvent, manufacturer Shell
BYK-310: Flow control additive, manufacturer BYK-Chemie
Paraloid B-66: Thermoplastic acrylate resin, manufacturer Dow Chemicals
DIDP: diisodecyl phthalate BYK-3550: flow control additive, manufacturer BYK-Chemie
Macrynal SM 510: 60% strength acrylate resin in butyl acetate, manufacturer Cytec
Dowanol PMA: 1-methoxy-2-propyl acetate, manufacturer Dow Chemicals
Solvent Naphtha: Aromatic solvent, manufacturer DHC Solvent Chemie
BYK-066N: Antifoam, manufacturer BYK-Chemie
BYK-306: Flow control additive, manufacturer BYK-Chemie
Desmodur N 75: Aliphatic polyisocyanate (HDI burette), 1-methoxy-2-propyl acetate medium strength 75%, manufacturer Bayer

  The white blends produced by the non-inventive comparative examples show higher ΔE values in all three systems tested, and thus lower pigment stability to flocculation and separation phenomena than the inventive examples. Show.

  For further evaluation of the compounds of the present invention, a powder coating with a polyester-based yellow color was made and applied to an aluminum Q-panel using an electrostatic powder gun at 80 kV / 2 bar. The panel was fired for 14 minutes at a circulating air temperature of 180 ° C. for curing. The evaluation was carried out with the gloss value at 20 °. The higher the value, the better the result. The numbers in the following formulas are in grams.

Claims (6)

Use of a polymer PAS containing amino groups or a salt thereof obtained by reaction with an acid,
The polymer is obtained by multistage synthesis, and in multistage synthesis,
Intermediate PA is prepared by reaction of amine A with compound P containing 2 to 6 epoxide groups and / or acrylic groups, and compound P is reactive towards hydroxyl and / or amino groups Containing 2 to 6 groups, amine A is
(I) primary and / or secondary amino groups with m = 1-8
(Ii) a hydroxyl group with n = 0-5, and (iii) a tertiary amino group with 1 = 0-5, where
(Iv) m + n ≧ 2,
(V) Amine A includes only a hydrocarbon group in addition to a nitrogen atom, an oxygen atom, and a hydroxyl group,
Intermediate PA is represented by the general formula (I)

[Where:
X ¹ = H or OH,
X ² = CH ₂ or C = O;
X ³ = O or NH]
Having structural units of
Intermediate PA is
(A) reacting with one or more components S that are reactive towards hydroxyl and / or amino groups to give polymers containing amino groups and / or (b) at least one lactone Or react with a mixture of lactones in a ring-opening polymerization to give a polymer containing amino groups, and (c) 0-80% of the primary and secondary amino groups originally present in the intermediate PA Reacting with one or more species of component U selected from the group of hydroxyl-functional acrylates and / or cyclic compounds selected from the group of oxiranes and oxetanes, lactones and cyclic carbonates, Occurs by the introduction of a hydroxyl group,
Component S is represented by the general formula (II)
Y—O—CO—NH—R ¹ NCO (II)
Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms, and Y reacts with an isocyanate. A monomer group or polymer group that is non-synthetic and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, and Y has a number average molar mass of less than 20000 g / mol ]
Containing an isocyanate adduct of
Component S is represented by the general formula (III)

Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms, and Y reacts with an isocyanate. A monomer group or polymer group that is non-synthetic and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, and Y has a number average molar mass of less than 20000 g / mol ]
Containing uretdione compounds, or
Component S is represented by the general formula (IV)
_{H 2 C = CH-COO-} Y (IV)
Wherein Y is a monomeric or polymeric group that is not reactive to isocyanate and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups; Has a number average molar mass of less than 20000 g / mol]
Containing acrylate, or
Component S comprises an acid selected from the group of carboxylic acids, phosphate esters, and sulfonic acids, and the polymer PAS is an intermediate PA, or one or more of the reactions (a), (b) and (c PA modified by the reaction of PA with the general formula (V), (VI) or (VII)
_{^{(HOOC) p -Y (X 1}} ) r (V)
(OH) _{3 -V} PO (OY (X ¹ ) _r ) _v (VI)
Y—SO ₂ —OH (VII)
[Wherein X ¹ = H or OH, p = 1-3, r = 1-5, v = 1 or 2, Y is not reactive to isocyanate, A monomeric or polymeric group comprising one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, Y has a number average molar mass of less than 20000 g / mol]
Obtained by reaction with a compound of
The polymer PAS comprises an intermediate PA or a PA modified by reaction of the PA according to one or more of the reactions (a), (b), and (c) and at least one lactone, or a mixture of lactones. Obtained by a reaction by ring-opening polymerization of
Said reactions of (a), (b), and (c) may be carried out in any desired combination and time series with each other, wetting agents, dispersants, emulsifiers, phase mediators (liquid / liquid compatibilization) Agents) use of polymer PAS containing amino groups or salts thereof obtained by reaction with acids. Manufacture or processing of dispersants, inks, coating materials, paints and varnishes, inks, paper coatings, leather and fiber dyes, pastes, pigment concentrates, manufacturing or processing of ceramics or cosmetics, synthetic, semi-synthetic or natural high Casting compositions and / or molding compositions based on molecular substances, PVC plastisol, gel coat, polymer concrete, printed circuit boards, industrial paints, wood and furniture varnishes, marine paints, anticorrosive paints, cans Manufacture of paints and coil paints, decorating paints, and architectural paints, solid concentrates such as pigment concentrates, inks for non-impact printing processes, color filters for liquid crystal displays, liquid crystal screens, color separation equipment , Sensor, plasma screen, SED (surface Conductive type electron emission display) and MLCC (multi-layer ceramic compound) display fabrication based on, or, for the manufacture of cosmetic products, obtained by reaction of the polymer PAS or acid containing an amino group described in claim 1 that Use of salt . Intermediate PA is an additional group in which the ethylenically unsaturated ester compound P to which the C═C double bond and the carbonyl double bond of the ester are conjugated is at least reactive to the ester, or a secondary Similar to the amino group, it contains at least two further groups that are reactive towards the ester, wherein the ethylenically unsaturated ester compound P is reacted by reaction with an amine similar to a diamine or primary amino group. Use of the polymer PAS containing amino groups according to claim 1 or 2 or a salt thereof obtained by reaction with an acid , characterized in that it can be prepared. Further groups that are reactive towards esters are primary or secondary amino groups and / or hydroxyl groups, polymer PAS comprising amino groups according to claim 3 or those obtained by reaction with acids. Use of salt . Intermediate PA is a dendritic polyamine which can be produced in a multi-stage reaction, in which the amine A or NH ₃ and the alkyl acrylate as component P are reacted with each other in the first stage and the reaction product in at least one further stage. Use of a polymer PAS containing amino groups or a salt thereof obtained by reaction with an acid according to claim 1, characterized in that it is reacted with a stoichiometric excess of diamine. A polymer PAS containing amino group-containing polymer PAS or a salt thereof obtainable by reaction with an acid, and obtained by multi-stage synthesis,
Intermediate PA is prepared by reaction of amine A with compound P containing 2 to 6 epoxide groups and / or acrylic groups, and compound P is reactive towards hydroxyl and / or amino groups Containing 2 to 6 groups, amine A is
(I) primary and / or secondary amino groups with m = 1-8
(Ii) a hydroxyl group with n = 0-5, and (iii) a tertiary amino group with 1 = 0-5, where
(Iv) m + n ≧ 2,
(V) Amine A includes only a hydrocarbon group in addition to a nitrogen atom, an oxygen atom, and a hydroxyl group,
Intermediate PA is represented by the general formula (I)

[Where:
X ¹ = H or OH,
X ² = CH ₂ or C = O;
X ³ = O or NH]
Having structural units of
Intermediate PA is
(A) reacting with one or more components S that are reactive towards hydroxyl and / or amino groups to give polymers containing amino groups and / or (b) at least one lactone Or react with a mixture of lactones in a ring-opening polymerization to give a polymer containing amino groups, and (c) 0-80% of the primary and secondary amino groups originally present in the intermediate PA Reacting with one or more species of component U selected from the group of hydroxyl-functional acrylates and / or cyclic compounds selected from the group of oxiranes and oxetanes, lactones and cyclic carbonates, Occurs by the introduction of a hydroxyl group,
Component S is represented by the general formula (II)
Y—O—CO—NH—R ¹ NCO (II)
Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms, and Y reacts with an isocyanate. A monomer group or polymer group that is non-synthetic and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, and Y has a number average molar mass of less than 20000 g / mol ]
Containing an isocyanate adduct of
Component S is represented by the general formula (III)

Wherein R ¹ is the same or different and is represented by a saturated or unsaturated, branched or unbranched organic group containing 6 to 20 carbon atoms, and Y reacts with an isocyanate. A monomer group or polymer group that is non-synthetic and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, and Y has a number average molar mass of less than 20000 g / mol ]
Containing uretdione compounds, or
Component S is represented by the general formula (IV)
_{H 2 C = CH-COO-} Y (IV)
Wherein Y is a monomeric or polymeric group that is not reactive to isocyanate and contains one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups; Has a number average molar mass of less than 20000 g / mol]
Containing acrylate, or
Component S comprises an acid selected from the group of carboxylic acids, phosphate esters and sulfonic acids, and the polymer PAS is an intermediate PA or one or more of the reactions (a), (b) and (c) above PA modified by the reaction of PA with the general formula (V), (VI), or (VII)
_{^{(HOOC) p -Y (X 1}} ) r (V)
(OH) _{3 -V} PO (OY (X ¹ ) _r ) _v (VI)
Y—SO ₂ —OH (VII)
[Wherein X ¹ = H or OH, p = 1-3, r = 1-5, v = 1 or 2, Y is not reactive to isocyanate, A monomeric or polymeric group comprising one or more aliphatic, cycloaliphatic, araliphatic and / or aromatic groups, Y has a number average molar mass of less than 20000 g / mol]
Or is reacted with
The polymer PAS comprises an intermediate PA or a PA modified by the reaction of a PA with one or more of the above reactions (a), (b), and (c), and at least one lactone or mixture of lactones Obtained by reacting in ring-opening polymerization,
A plastic comprising the polymer PAS, wherein the reactions of (a), (b), and (c) may be carried out in any desired combination and time series with each other.